An efficient and facile synthesis of 3-aryl-1,5-pentanedione derivatives under solvent-free conditions

Article abstract of DOI:10.1007/s11164-015-2082-6

An efficient synthesis of 3-aryl-1,5-pentanedione derivatives from the reaction of aromatic aldehydes and 1,2-diphenylethanone has been reported. Although 3-aryl-1,5-pentanedione is a frequently used synthetic intermediate, few mature methods have been re

Full text of DOI:10.1007/s11164-015-2082-6

Res Chem Intermed
DOI 10.1007/s11164-015-2082-6
An efficient and facile synthesis of 3-aryl-1,5-
pentanedione derivatives under solvent-free conditions
Yunyun Zha1 Zhiying Meng1 Mengyao Wang1
•
•
•
Mengmeng Gu1 Chuan Li1 Peijun Cai2
Liangce Rong1
•
•
•
Received: 8 January 2015 / Accepted: 24 April 2015
Ó Springer Science+Business Media Dordrecht 2015
Abstract An efficient synthesis of 3-aryl-1,5-pentanedione derivatives from the
reaction of aromatic aldehydes and 1,2-diphenylethanone has been reported.
Although 3-aryl-1,5-pentanedione is a frequently used synthetic intermediate, few
mature methods have been reported for the synthesis of this kind of derivative. In
our research, this reaction could be carried out smoothly promoted by NaOH under
solvent-free conditions. Because of the low cost, and readily available reagent,
NaOH is an efficient catalyst for the synthesis of these dione compounds. The other
advantages of this procurement are high yields, simple operation, atomic economy,
mild reaction conditions, and environmental friendliness. The d-D structure has
been additional confirmed by X-ray diffraction analysis.
Keywords 1,5-Pentanedione Á 1,2-Diphenylethanone Á Solvent-free Á
Green synthesis Á Environmental friendliness
Electronic supplementary material The online version of this article (doi:10.1007/s11164-015-2082-6)
contains supplementary material, which is available to authorized users.
&
&
1
Peijun Cai
caipj@163.com
Liangce Rong
lcrong2005@yahoo.com
College of Chemistry and Chemical Engineering, Xuzhou Normal University, Jiangsu Key
Laboratory of Green Synthetic Chemistry for Functional Materials, Xuzhou 221116, Jiangsu,
People’s Republic of China
2
School of Chemical Engineering and Technology, China University of Mining and Technology,
Xuzhou 221006, Jiangsu, People’s Republic of China
123

Y. Zha et al.
Introduction
The open-chain 1,5-pentanedione compounds are important intermediates in organic
synthesis chemistry, which always involves synthesis of piperidine and pyran
compounds [1–3]. Under investigation, it was found that few in the literature have
reported the synthesis of these 1,5-pentanedione derivatives.
Green chemistry techniques become a major challenge for chemists that aim to
conserve resources and minimize economic burden [4, 5]. In recent years, many new
methods and techniques have been developed for green synthesis chemistry, such as
ionic liquid synthesis [6–8], the ultrasonic technique [9–11], the microwave
irradiation technique [12, 13], and solvent-free organic synthesis [4, 14–17]. Because
of its simple operation, ease of control, and convenient disposition, solvent-free
synthesis is the most efficient approach for application in many classic reactions, for
example, the Grignard reaction [18], the Reformatsky reaction [19, 20], aldol
condensations [21–24], Dieckmann condensations [25], the phenol coupling reaction
[26–28], the reduction reaction [29–31], peptide bond formation [32], and so on.
In this article, we report an efficient and facile process for preparation of open-
chain 1,5-pentanedione derivatives under solvent-free conditions.
Results and discussion
Before our research, we investigated the reported methods for the synthesis of this
kind of compound. Beyond our expectations, few papers were found to synthesize
similar 3-aryl-1,5-pentanedione derivatives. It could be definitely confirmed that
Lantan˜o [33] had reported synthesizing the similar 1,5-pentanedione using the
strong base (MeONa) as a catalyst. This reaction condition was harsh because of
anhydrous EtOH and the long reaction time (72 h). Bagavant [34] also reported a
process to prepare similar products in MeONa/MeOH after about 20 h. These
approaches both needed a strong base (MeONa), a long reaction time, and organic
solvent. So, it is necessary to find an efficient and facile approach for synthesis of
open-chain 1,5-pentanedione derivatives. Because of the advantages of solvent-free
synthesis, we planned to carry out our research under solvent-free conditions.
In order to implement our research plan, 4-fluorobenzaldehyde 1a (1 mmol) and
1,2-diphenylethanone 2 (2 mmol) were chosen as standard substrates for optimizing
the reaction conditions, and various parameters were studied, such as the catalysts,
temperature, and reaction time (Table 1) by grinding starting materials in a mortar. As
shown in Table 1, when acid catalysts such as B(OH)3, ZnCl2, P-TSA (p-
toluenesulfonic acid), NH2SO3H, or a weak base such as K2CO3, Na2CO3 were used
in model reactions, the products were not found or they had very low yields (Table 1,
Entry 1–6). However, when strong alkali (NaOH) was used in this operation, the
reaction could be carried out smoothly with a good yield (Table 1, Entry 7). As the
amount of NaOH was 0.1 g, the reaction time was about 15 min, and room
temperature (r.t.), it gave the best yield (Table 1, Entry 9). Higher temperatures did not
improve the yields (Table 1, Entry 11, 12). Similar, longer reaction times were no help
for the yields (Table 1, Entry 10, 11). Different amounts of NaOH were also studied in
123

An efficient and facile synthesis of…
Table 1 Optimization of the reaction of 4-fluorobenzaldehyde and 1,2-diphenylethanone
F
O
O
O
Grinding
O
H
Ph
Ph
Ph
2
Solvent-free
Ph
Ph Ph
F
1a
3a
2
Entry
Conditions
Catalyst
Yield (%)a
Catalyst amount (g)
Temperature (°C)
Time (min)
1
B(OH)3
ZnCl2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.1
0.1
0.1
0.1
0.1
0.3
0.4
0.1
0.2
0.1
0.1
r.t.
r.t.
r.t.
r.t.
55
55
r.t.
r.t.
r.t.
r.t.
50
70
r.t.
r.t.
r.t.
r.t.
r.t.
70
10
10
10
10
10
10
10
10
15
30
30
30
15
15
15
15
60
60
None
None
None
None
Trace
Trace
61
2
3
P-TSA
NH2SO3H
K2CO3
Na2CO3
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
KOH
4
5
6
7
8
89
9
92
10
11
12
13
14
15
16
17
18
91
90b
91b
50
45
87
KOH
58
NaOH (EtOH)
NaOH (EtOH)
None
None
General reaction condition: the reactions were carried out using 4-fluorobenzaldehyde 1a (1 mmol) and
1,2-diphenylethanone (2 mmol) and several kinds of catalysts
a
Isolated yields
b
After grinding, the mixture was transferred into a flask and heated at 70 °C for the reaction
this reaction, it showed the yields were gradually reduced with the increase loading of
NaOH (Table 1, Entry 7, 8, 14, 15). It could be explained that more NaOH could turn
the reagents into solid more quickly, which hindered the reaction from going to
completion. The other stronger base, KOH, could also promote the reaction, but the
effect was the same as NaOH. The reaction was also checked in EtOH, but no product
was found (Table 1, Entry 17, 18). So, solvent-free, NaOH (0.1 g), room temperature,
and 15 min were the preferred reaction conditions.
Under the optimized conditions, different aromatic aldehydes with different
substituted groups were reacted with 1,2-diphenylethanone under a solvent-free
condition to expand the scope of the reaction, and all reactions could be carried out
smoothly, and corresponding products could be obtained with high yields
123

Y. Zha et al.
Table 2 Synthesis of 3-aryl-1,5-pentanedione derivatives under a solvent-free condition
R
O
O
O
O
NaOH
Solvent-free
H
Ph
Ph
Ph
R
2
Ph
Ph Ph
1
3
2
Entry
R
Product
Time (min)
Yield (%)a
1
4-F
3a
3b
3c
3d
3e
3f
15
20
10
10
15
10
20
15
10
92
85
93
90
88
87
91
92
93
2
3-Cl
4-Cl
3
4
3,4-Cl2
3-Br
5
6
4-Br
7
4-CH3
3g
3h
3j
8
4-CH3O
3,4-OCH2O
10
General reaction condition: different aromatic aldehydes 1 (1 mmol), 1,2-diphenylethanone 2 (2 mmol)
and 0.1 g NaOH as catalyst under a solvent-free condition at r.t
a
Isolated yields
(85–93 %). The results are summarized in Table 2. As shown in Table 2, the
aldehydes bearing either electron-withdrawing or electron-donating groups perform
well in this reaction. Therefore, we could conclude the electronic nature of the
substituted groups has no significant effect on this reaction.
1
The structures of the products derivatives were characterized by their IR, H
NMR, 13C NMR, and HRMS spectra. We take 3a as an example to analyze their
structure. In its IR, the wave numbers at 1675 and 1596 cm-1 are the signals of
1
carbonyl (C=O). In its H NMR, The triplet signal at d = 4.18 (1H, J = 10.4 Hz)
ppm is due to the tertiary hydrogen of C-3. The doublet signals at 5.51 (1H,
J = 9.6 Hz) and 5.60 (1H, J = 10.8 Hz) are the two protons of C-2 and C-4. The
products have four stereoisomers: two meso forms (A, B) and one pair of
enantiomers(C, D) (Fig. 1). However, the structures must not be the two mesomers
A or B. Because the mesomers A or B have planes of symmetry, leading to the same
chemical environment of C-2 and C-4, their attached hydrogen atoms will have
identical chemical shifts in NMR spectra. So the structure may be C or D.
Fortunately, we obtained the crystal structure of the product 3d. With the help of
X-diffraction, we could confirm the product was the structure of the C (see in
Fig. 2). The absolute configuration of the product is ‘‘2R’’ and ‘‘4R.’’ We did not
find its enantiomer D (2S, 4S). This condition may be a result of the characteristic of
a solvent-free reaction. This analysis results can be found in [33].
The phenyl protons are distributed from 6.78 to 7.83 ppm. In its 13C NMR, the
chemical shifts of the 35 carbon atoms are at 49.5, 55.1, 58.8, 113.8, 114.0, 126.2,
123

An efficient and facile synthesis of…
Fig. 1 Stereoisomers of
products
O
H
Ar
Ph
Ph
O
Ph
O
Ph
O
Ph
Ph
H
H
Ph
H
H
H
Ar
Ph
Ph
Ar
Ph
H
H
H
Ph
H
Ph
H
Ar
H
O
Ph
O
Ph
O
Ph
O
Ph
(2R, 4R)
(2S, 4S)
A
B
C
D
enantiomer
mesomers
Fig. 2 The crystal-structure of 3d
127.3, 127.8, 128.0, 128.1, 128.6, 129.6, 130.5, 132.5, 133.1, 135.5, 136.2, 137.7,
138.2, 158.8, 161.2, 197.2, and 198.2, respectively. In the HR mass spectrum, the
calculated and found values of m/z for C35H27F [M ? H]?: 467.2170, and
467.2155. The structure of 3d was also confirmed by X-ray diffraction analysis; the
crystal structure 3d is shown in Fig. 2.
123

Y. Zha et al.
Conclusions
In summary, we have reported an efficient and convenient method for preparation of
3-aryl-1,5-pentanedione derivatives by grinding aromatic aldehydes and 1,2-dipheny-
lethanone under solvent-free conditions. As this uses inexpensive and easily available
NaOH as catalyst, this was an attractive approach to give open-chain 1,5-pentanedione
derivatives. Furthermore, a solvent-free condition have other advantages, such as good
yields, lower cost, reduced environmental impact, and simple operation.
Experimental
All reactions were performed at room temperature under air atmosphere on an agate
mortar. The melting points were metered on an XT-5 micro melting point apparatus
and were uncorrected. IR spectra were obtained from a FT Bruker Tensor 27
spectrometer using KBr as background. 1H NMR (400 MHz) and 13C NMR
(100 MHz) spectra were recorded under solution in DMSO-d6 or CDCl3 using a
Bruker NMR spectrometer with TMS as an internal standard. HRMS were measured
with a Bruker microTOF-Q134 instrument. All reagents were purchased commer-
cially and used without further purification. X-ray diffractions were recorded on a
Siemens P4 or Simart-1000 diffractometer.
General procedure for the synthesis of 3-aryl-1,5-pentanedione
The mixture of aromatic aldehydes 1 (1 mmol), 1,2-diphenylethanone 2 (2 mmol)
and 0.1 g NaOH was added into a mortar. Then, the mixture was ground at room
temperature about 10–20 min and the solid was formed. The solid was pour into
water and soaked for 30 min, and the products were floated on the water. Then,
filtered, and then washed twice with 10 mL of water thoroughly. The separated solid
was dried and recrystallized from 95 % ethanol.
3-(4-Fluorophenyl)-1,2,4,5-tetraphenylpentane-1,5-dione (3a)
m.p. 210–212 °C; IR (KBr, m, cm-1): 1675, 1596, 1579, 1509, 1491, 1448, 1264,
1227, 1177, 1078, 1003, 979, 825, 758, 693, 548 cm-1 1H NMR (400 MHz,
;
DMSO-d6) (d, ppm): 4.84 (1H, t, J = 10.4 Hz, CH), 5.51 (1H, d, J = 9.6 Hz, CH),
5.60 (1H, d, J = 10.8 Hz, CH), 6.78 (2H, t, J = 8.8 Hz, ArH), 6.85–6.92 (4H, m,
ArH), 6.99 (2H, t, J = 7.2 Hz, ArH), 7.12 (2H, d, J = 7.6 Hz, ArH), 7.31 (2H, t,
J = 7.6 Hz, ArH), 7.37 (3H, t, J = 7.6 Hz, ArH), 7.43–7.50 (5H, m, ArH), 7.66
(2H, d, J = 7.2 Hz, ArH), 7.83 (2H, d, J = 7.2 Hz, ArH);13C NMR (100 MHz,
DMSO-d6) (d, ppm):49.5, 55.1, 58.8, 113.8, 114.0, 126.2, 127.3, 127.8, 128.0,
128.1, 128.6, 129.6, 130.5, 132.5, 133.1, 135.5, 136.2, 137.7, 138.2, 158.8, 161.2,
197.2, 198.2; HRMS m/z calculated for C35H27F [M ? H]?: 467.2170, found:
467.2155.
123

An efficient and facile synthesis of…
3-(3-Chlorophenyl)-1,2,4,5-tetraphenylpentane-1,5-dione (3b)
m.p. 218–219 °C; IR (KBr, m, cm-1): 1672, 1596, 1571, 1491, 1448, 1265, 1193,
1174, 1079, 1003, 975, 785, 693, 629, 542, 516 cm-1; 1H NMR (400 MHz, CDCl3)
(d, ppm): 4.84 (1H, dd, J = 2.4 Hz, J = 7.6 Hz, CH), 5.06 (1H, d, J = 7.6 Hz,
CH), 5.19 (1H, d, J = 10.0 Hz, CH), 6.89 (2H, d, J = 5.2 Hz, ArH), 6.96–6.99 (1H,
m, ArH), 7.01–7.06 (5H, m, ArH), 7.12 (3H, t, J = 7.6 Hz, ArH), 7.21–7.27 (5H, m,
ArH), 7.37 (4H, t, J = 7.2 Hz, ArH), 7. 60 (2H, d, J = 7.6 Hz, ArH), 7.72 (2H, d,
J = 7.2 Hz, ArH); 13C NMR (100 MHz, DMSO-d6) (d, ppm):49.9, 54.8, 58.4,
125.6, 126.4, 127.3, 127.9, 128.1, 128.7, 129.6, 130.4, 132.0, 132.6, 133.2, 135.3,
135.5, 136.1, 137.4, 144.6, 196.9, 198.0; HRMS m/z calculated for C35H27Cl
[M ? Na]?: 505.1694, found: 505.1701.
3-(4-Chlorophenyl)-1,2,4,5-tetraphenylpentane-1,5-dione (3c)
m.p. 229–230 °C; IR (KBr, m, cm-1): 1672, 1597, 1579, 1492, 1447, 1267, 1177,
984, 823, 754, 701, 689, 609, 545 cm-1 1H NMR (400 MHz, DMSO-d6) (d,
;
ppm):4.84 (1H, t, J = 10.4 Hz, J = 10.0 Hz, CH), 5.52 (1H, d, J = 9.6 Hz, CH),
5.60 (1H, d, J = 10.8 Hz, CH), 6.84–6.91 (4H, m, ArH), 7.01 (4H, dd, J = 2.4 Hz,
J = 7.6 Hz, ArH), 7.13 (2H, d, J = 7.6 Hz, ArH), 7.31 (2H, t, J = 7.6 Hz, ArH),
7.37 (2H, t, J = 7.6 Hz, ArH), 7.42–7.48 (6H, m, ArH), 7.66 (2H, d, J = 7.6 Hz,
ArH), 7.83 (2H, d, J = 7.2 Hz, ArH); 13C NMR (100 MHz, DMSO-d6) (d, ppm):
49.5, 54.8, 58.6, 126.3, 127.2, 127.9, 128.0, 128.7, 129.6, 130.0, 130.4, 132.6,
133.1, 135.3, 136.0, 137.5, 141.2, 197.0, 198.0; HRMS m/z calculated for
C35H27Cl[M ? Na]?: 505.1694, found: 505.1703.
3-(3,4-Dichlorophenyl)-1,2,4,5-tetraphenylpentane-1,5-dione (3d)
m.p. 230–231 °C; IR (KBr, m, cm-1): 1672, 1596, 1579, 1492, 1472, 1448, 1399,
1
1296, 1267, 1194, 1175, 1128, 1028, 1003, 984, 828, 754, 693, 623, 526 cm-1; H
NMR (400 MHz, DMSO-d6) (d, ppm):4.82 (1H, t, J = 10.0 Hz,CH), 5.55 (1H, d,
J = 9.6 Hz, CH), 5.64 (1H, d, J = 10.4 Hz, CH), 6.84–6.93 (4H, m, ArH), 7.03
(2H, t, J = 7.2 Hz, ArH), 7.15 (2H, d, J = 7.2 Hz, ArH), 7.23 (1H, d, J = 8.0 Hz,
ArH), 7.32 (3H, t, J = 7.6 Hz, ArH), 7.37–7.44 (5H, m,ArH), 7.47 (2H, t,
J = 7.2 Hz, ArH), 7.67 (2H, d, J = 7.6 Hz, ArH), 7.85 (2H, d, J = 7.2 Hz, ArH);
13C NMR (100 MHz, DMSO-d6) (d, ppm): 49.5, 54.8, 58.7, 126.3, 127.2, 127.9,
128.1, 128.7, 129.6, 130.0, 130.4, 132.6, 133.1, 135.3, 136.0, 137.5, 141.2, 197.0,
198.0; HRMS m/z calculated for C35H26Cl2 [M ? H]?: 517.1484, found: 517.1492.
3-(3-Bromophenyl)-1,2,4,5-tetraphenylpentane-1,5-dione (3e)
m.p. 215–216 °C; IR (KBr, m, cm-1): 1673, 1596, 1566, 1491, 1448, 1265, 1193,
1175, 1072, 975, 784, 698, 629, 542, 515 cm-1; 1H NMR (400 MHz, DMSO-d6) (d,
ppm):4.80 (1H, t, J = 10.0 Hz,CH), 5.53 (1H, d, J = 9.6 Hz, CH), 5.63 (1H, d,
J = 10.8 Hz, CH), 6.83–6.93 (5H, m, ArH), 7.00 (3H, t, J = 7.6 Hz, ArH), 7.12
(2H, d, J = 7.6 Hz, ArH), 7.31 (3H, t, J = 7.6 Hz, ArH), 7.38 (3H, t, J = 8.0 Hz,
123

Y. Zha et al.
ArH), 7.43–7.51 (4H, m,ArH), 7.67 (2H, d, J = 7.6 Hz, ArH), 7.84 (2H, d,
J = 7.6 Hz, ArH); 13C NMR (100 MHz, DMSO-d6) (d, ppm): 49.5, 54.8, 58.4,
126.4, 127.3, 128.0, 128.5, 129.2, 129.6, 130.4, 132.6, 133.2, 135.3, 135.5, 136.1,
137.4, 144.8, 196.9, 198.0; HRMS m/z calculated for C35H27Br [M ? H]?:
527.1369, found: 527.1364.
3-(4-Bromophenyl)-1,2,4,5-tetraphenylpentane-1,5-dione (3f)
m.p. 240–242 °C; IR (KBr, m, cm-1): 1680, 1596, 1579, 1490, 1446, 1267, 1178,
1076, 1008, 983, 819, 697, 681, 607, 543 cm-1; 1H NMR (400 MHz, DMSO-d6) (d,
ppm): 4.82 (1H, t, J = 10.0 Hz, CH), 5.52 (1H, d, J = 9.6 Hz, CH), 5.60 (1H, d,
J = 10.8 Hz, CH), 6.84–6.91 (4H, m, ArH), 6.99 (2H, t, J = 7.6 Hz, ArH), 7.14
(4H, dd, J = 4.4 Hz, J = 8.8 Hz, ArH), 7.31 (3H, t, J = 7.6 Hz, ArH), 7.37 (3H, t,
J = 7.6 Hz,ArH), 7.42–7.50 (4H, m, ArH), 7.66 (2H, d, J = 7.6 Hz, ArH), 7.83
(2H, d, J = 7.6 Hz, ArH); 13C NMR (100 MHz, DMSO-d6) (d, ppm): 50.5, 55.7,
58.4, 120.2, 127.2, 127.9, 128.2, 128.4, 128.5, 129.0, 130.2, 130.3, 130.6, 132.0,
132.7, 132.9, 136.4, 136.6, 136.7, 137.2, 139.5, 199.7, 199.8; HRMS m/z calculated
for C35H27Br [M ? Na]?: 549.1188, found: 549.1186.
1,2,4,5-Tetraphenyl-3-(p-tolyl)pentane-1,5-dione (3g)
m.p. 235–236 °C; IR (KBr, m, cm-1): 1681, 1597, 1580, 1513, 1492, 1447, 1267,
1179, 1034, 1002, 982, 813, 755, 696, 616, 548 cm-1; 1H NMR (400 MHz, CDCl3)
(d, ppm): 2.11 (3H, s, CH3), 4.81 (1H, dd, J = 3.6 Hz, J = 7.2 Hz, CH), 5.02 (1H,
d, J = 7.2 Hz, CH), 5.20 (1H, d, J = 10.4 Hz, CH), 6.78 (2H, d, J = 7.6 Hz, ArH),
6.94 (2H, d, J = 8.0 Hz, ArH), 7.01–7.08 (7H, m, ArH), 7.14 (2H, t, J = 7.2 Hz,
ArH), 7.24 (3H, t, J = 7.6 Hz, ArH), 7.36 (2H, t, J = 8.8 Hz, ArH), 7.42 (2H, d,
J = 7.6 Hz, ArH), 7.60 (2H, d, J = 7.6 Hz, ArH), 7.71 (2H, d, J = 7.6 Hz, ArH);
13C NMR (100 MHz, DMSO-d6) (d, ppm): 54.9, 55.3, 55.4, 56.4, 110.6, 111.9,
113.2, 119.0, 120.1, 122.3, 126.3, 127.3, 127.9, 128.2, 128.6, 129.0, 129.2, 129.6,
131.0, 131.5, 134.1, 137.2, 137.7, 139.2, 147.2, 148.8, 152.2, 162.2, 165.0, 165.9,
171.3;HRMS m/z calculated for C36H30 [M ? H]?: 463.2420, found: 463.2413.
3-(4-Methoxyphenyl)-1,2,4,5-tetraphenylpentane-1,5-dione (3h)
m.p. 237–238 °C; IR (KBr, m, cm-1): 1670, 1597, 1580, 1513, 1492, 1449, 1342,
1303, 1265, 1177, 1111, 1035, 1004, 984, 826, 755, 697, 613, 547 cm-1; 1H NMR
(400 MHz, CDCl3) (d, ppm): 3.64 (3H, s, OCH3), 4.79 (1H, dd, J = 3.6 Hz,
J = 7.2 Hz, CH), 5.01 (1H, d, J = 7.2 Hz, CH), 5.18 (1H, d, J = 10.4 Hz, CH),
6.52 (2H, d, J = 8.8 Hz, ArH), 6.97 (2H, d, J = 8.4 Hz, ArH), 7.00–7.09 (6H, m,
ArH), 7.15 (2H, t, J = 7.2 Hz, ArH), 7.22–7.26 (4H, m, ArH), 7.36 (2H, t,
J = 7.2 Hz, ArH), 7.42 (2H, d, J = 7.6 Hz,ArH), 7.60 (2H, d, J = 7.6 Hz, ArH),
7.71 (2H, d, J = 7.2 Hz, ArH); 13C NMR (100 MHz, DMSO-d6) (d, ppm): 49.3,
54.5, 55.2, 59.0, 112.6, 126.1, 127.2, 127.8, 128.0, 128.6, 129.7, 130.5, 132.5,
133.0, 133.9, 135.6, 136.2, 137.9, 156.7, 197.5, 198.1;HRMS m/z calculated for
C36H30O [M ? H]?: 479.2369, found: 479.2378.
123

An efficient and facile synthesis of…
1,2,4,5-Tetraphenyl-3-(4-(pyridin-4-yl)phenyl)pentane-1,5-dione (3i)
m.p. 220–222 °C; IR (KBr, m, cm-1): 1672, 1597, 1578, 1559, 1491, 1449, 1267,
1
1173, 985, 762, 693, 606, 556, 540 cm-1; H NMR (400 MHz, DMSO-d6) (d,
ppm):4.83 (1H, t, J = 10.4 Hz, CH), 5.56 (1H, d, J = 9.6 Hz, CH), 5.66 (1H, d,
J = 10.8 Hz, CH), 6.87–6.93 (4H, m, ArH), 6.99 (2H, t, J = 7.6 Hz, ArH), 7.15
(2H, d, J = 7.6 Hz, ArH), 7.30–7.40 (6H, m, ArH), 7.43–7.49 (4H, m, ArH), 7.67
(2H, d, J = 7.6 Hz, ArH), 7.84 (2H, d, J = 7.6 Hz, ArH), 8.14 (2H, d, J = 5.2 Hz,
ArH); 13C NMR (100 MHz, DMSO-d6) (d, ppm): 49.3, 54.5, 55.2, 59.0, 112.6,
126.1, 127.2, 127.8, 128.0, 128.6, 129.7, 130.5, 132.5, 133.0, 133.9, 135.6, 136.2,
137.9, 156.7, 197.5, 198.1; HRMS m/z calculated for C34H27N [M ? H]?:
450.2216, found: 450.2209.
3-(Benzo[d][1,3]dioxol-5-yl)-1,2,4,5-tetraphenylpentane-1,5-dione (3j)
m.p. 231–233 °C; IR (KBr, m, cm-1): 1669, 1557, 1519, 1505, 1443, 1370, 1316,
1
1240, 1198, 1039, 811, 769, 699 cm-1; H NMR (400 MHz, DMSO-d6) (d, ppm):
4.24 (1H, d, J = 13.6 Hz, CH), 4.45 (1H, d, J = 13.6 Hz, CH), 5.30 (1H, s, CH),
6.03 (2H, s, OCH2O), 6.84–6.91 (6H, m, ArH), 7.06–7.11 (5H, m, ArH), 7.24–7.27
(12H, m, ArH); 13C NMR (100 MHz, DMSO-d6) (d, ppm): 49.8, 55.2, 58.5, 100.3,
101.2, 107.4, 108.4, 111.1, 120.6, 126.4, 127.2, 127.8, 128.0, 128.5, 129.0, 129.7,
130.6, 132.5, 133.0, 133.6, 135.5, 136.5, 137.3, 144.6, 146.3, 147.0, 147.7, 173.4,
197.3, 198.0; HRMS m/z calculated for C36H28O2 [M ? Na]?: 515.1987, found:
515.1992.
Acknowledgments We are grateful to the National Natural Science Foundation of China (NSFC, No.
51174201), the Open Foundation of Southwest University of Science and Technology (No. K201312),
and the Priority Academic Program Development of Jiangsu Higher Education Institutions for financial
support.
References
1. T.I. Akimova, N.S. Kravchenko, A.V. Gerasimenko, V.A. Denisenko, V.I. Vysotskii, Tetrahedron
Lett. 53, 5933 (2012)
2. T. Nakajima, D. Yamashita, K. Suzuki, A. Nakazaki, T. Suzuki, S. Kobayashi, Org. Lett. 13, 2980
(2011)
3. T.I. Akimova, N.S. Kravchenko, V.A. Denisenko, Tetrahedron 64, 9548 (2008)
4. M.A.P. Martins, C.P. Frizzo, D.N. Moreira, L. Buriol, P. Machado, Chem. Rev. 109, 4140 (2009)
5. P. Anastas, N. Eghbalia, Chem. Soc. Rev. 39, 301 (2010)
6. C. Yuan, X. Gao, Z. Pan, X. Li, Z. Tan, Catal. Commun. 58, 215 (2015)
7. N. Azgomi, M. Mokhtary, J. Mol. Catal. A: Chem. 398, 58 (2015)
8. S.M. Sadeghzadeh, F. Daneshfar, J. Mol. Liq. 199, 440 (2014)
9. M. Rouhani, A. Ramazani, S.W. Joo, Ultrason. Sonochem. 22, 391 (2015)
10. M.N. Rashin, J. Hemalatha, J. Mol. Liq. 197, 257 (2014)
11. J. Safari, Z. Zarnegar, J. Mol. Struct. 1072, 53 (2014)
12. M.A.E.A.A.A.E. Remaily, S.K. Mohamed, Tetrahedron 70, 270 (2014)
13. B. Zhao, Y. Xua, Q.G. Deng, Z. Liu, L.Y. Wang, Y. Gao, Tetrahedron Lett. 55, 4521 (2014)
14. G. Harichandrana, S.D. Amalraja, P. Shanmugamb, J. Mol. Catal. A: Chem. 392, 31 (2014)
123

Y. Zha et al.
15. S. Mahernia, M. Adi, M. Mahdavi, M. Nosrati, Tetrahedron Lett. 55, 3844 (2014)
´
16. J.G. Hernandez, E. Juaristi, Chem. Commun. 48, 5396 (2012)
´
17. J.G. Hernandez, C.G. Avila-Ortiz, E. Juaristi, Useful chemical activation alternatives in solvent-free
organic reactions, in Comprehensive Organic Synthesis, 2nd edn, ed. by G.A. Molander, P. Knochel
(Elsevier, Oxford), vol. 9, pp. 287–314 (2014)
18. M. Gao, N.N. Patwardhan, P.R. Carlier, J. Am. Chem. Soc. 135, 14390 (2013)
19. C.A. de Souzaa, R.F.M. de Souzab, M. Navarroa, I. Malvestiti, A.P.F. da Silva, L.W. Bieber, M.C.C.
Areias, Electrochim. Acta 89, 631 (2013)
20. X. Chen, C. Zhang, H. Wu, X. Yu, W. Su, Synthesis 20, 3233 (2007)
21. A.R. Gholap, A.P. Chavan, J. Chem. Res. 6, 374 (2003)
22. F. Chen, N. Li, S.S. Li, J.F. Yang, X. Chen, C. Zhang, H. Wu, X. Yu, W. Su, J. Cheng, Catal.
Commun. 59, 229 (2015)
23. S.M. Islam, A.S. Roy, R.C. Dey, S. Paul, J. Mol. Catal. A: Chem. 394, 66 (2014)
´
24. J.G. Hernandez, E. Juaristi, J. Org. Chem. 76, 1464 (2011)
25. J.E. Horta, J. Chem. Educ. 88, 1014 (2011)
26. F. Toda, T. Suzuki, S. Higa, J. Chem. Soc. 21, 3521 (1998)
27. T.K. Achar, P. Mal, J. Org. Chem. 80, 666 (2015)
28. W.Y. Yin, H.F. He, Y.N. Zhang, D. Luo, H.W. He, Synthesis 46, 2617 (2014)
29. A.C. Shekhar, A.R. Kumar, G. Sathaiah, K. Raju, P.S. Rao, M. Sridhar, B. Narsaiah, P.V.S.S.
Srinivas, B. Sridhar, Helv. Chim. Acta 95, 502 (2012)
30. R. Khajuria, K.K. Kapoor, Curr. Microw. Chem. 1, 110 (2014)
31. A.S. Touchy, S.M.A.H. Siddiki, K. Kon, K. Shimizu, ACS Catal. 4, 3045 (2014)
32. Q.P.B. Nguyen, T.H. Kim, Tetrahedron 69, 4938 (2013)
33. J.D. Mufato, D.R. Vega, J.M. Aguirre, D.J. dela Faba, B. Lantan˜o, J. Mol. Struct. 987, 119 (2011)
34. P. Paranjpe, G.J. Bagavant, Indian Chem. Soc. 49, 589 (1972)
123